Inspired by the concept of organic waste valorisation and heading towards a sustainable economy, a green chemistry extraction technique involving supercritical carbon dioxide (SC-CO2) along with water as a cosolvent was employed for the main winery by-product (grape pomaces). The objective was to selectively extract high-value added molecules, in particular phenolic compounds and polysaccharides. The experimental design involved applying three distinct temperature conditions (40, 60, and 80 °C), and a constant pressure of 400 bar. Phenolic compounds and high-molecular weight isolates (449-478 kDa) containing low methoxyl (% DE = 23) pectic substances were detected in the SC-CO 2 extracts accompanied by water as a co-solvent. The phenolic acids, namely, gallic (GA), protocatechuic (PCA), coumaric (CouA), and caftaric (CTA), and flavonoids, namely, procyanidin B1 (PRC B1), procyanidin B 2 (+) (PRC B 2), (+) catechin (CT), and (−) epicatechin (ECT) were found in all the extracts under the tested experimental conditions. The following study underscores the potential of the pressurized CO 2 /H 2 O medium as an effective solvent with minimal environmental impacts for the comprehensive valorisation of the main winery by-product, specifically targeting polysaccharides and phenolic compounds. Sustainability spotlight This study focuses on the extraction of valuable molecules such as polyphenols and bers from grape pomace, a by-product of wine production, using a green chemistry technique called supercritical uid extraction. These extracted molecules have potential applications as antioxidants in wine production. The research highlights the signicance of specic United Nations sustainable development goals, including affordable and clean energy (SDG 7), industry, innovation, and infrastructure (SDG 9), and climate action (SDG 13).